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Beta-naphthyl methyl substituted spiral bisoxazoline ligand, synthetic method and application thereof

A bisoxazoline and spiro ring technology is applied in the field of β-naphthylmethyl substituted spirocyclic bisoxazoline ligands, which can solve problems such as unsatisfactory effects, achieve good industrial and pharmaceutical application prospects, and high catalytic activity. and chirality-inducing effects, good generalizability and functional group tolerance

Active Publication Date: 2012-05-09
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the ligand is still not ideal for the high enantioselective synthesis of optically active indolanes
Therefore, further modification and exploration of this kind of ligands still need to be carried out.

Method used

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  • Beta-naphthyl methyl substituted spiral bisoxazoline ligand, synthetic method and application thereof
  • Beta-naphthyl methyl substituted spiral bisoxazoline ligand, synthetic method and application thereof
  • Beta-naphthyl methyl substituted spiral bisoxazoline ligand, synthetic method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036]

[0037] Under inert gas protection, add 100mg (R a )-1, 160 mg aminoalcohol, 289 mg DCC and 94 mg nitrogen hydroxybenzotriazole. Add 10 mL of tetrahydrofuran under ice-cooling, keep at 0°C for 0.5-20 hours, then naturally rise to room temperature, react overnight, and TLC detects that the reaction is complete (petroleum ether: ethyl acetate = 1:1). The solvent was removed under reduced pressure, and the product was directly used in the next reaction by short column filtration.

[0038] Add 4 mg of DMAP to the reaction tube containing the product obtained in the previous step. After ventilation, add 5 mL of dichloromethane, add 0.3 mL of triethylamine under ice bath, add 143 mg of methanesulfonyl chloride after stirring for a while, and keep at 0 ° C for 0.5 After -5 hours, add 1.0 mL of triethylamine, let it rise to room temperature naturally, and react overnight, and TLC detects that the reaction is complete. Directly spin off solvent, column chromatography obtai...

Embodiment 2

[0041]

[0042] R 1 = H, R 2 = H, R 3 = n-heptyl

[0043] Pd(dba) 2 (6mg, 0.011mmol) and (R a , S, S)-3 (7mg, 0.011mmol) (ligand synthesized in Example 1) was complexed in 1mL tetrahydrofuran for 0.5-10 hours, then added Ag 3 PO 4 (34mg, 0.081mmol), 4a (75mg, 0.20mmol), 5a (112mg, 0.81mmol) and 1mL tetrahydrofuran. The reaction was reacted at 0-200°C, TLC followed the completion of the reaction, and directly spin-dried column chromatography to obtain a colorless viscous Thick liquid 44mg. (R)-6aa (57%, 96% ee): [α] 20 D =+9.4 (c=0.50, ethyl acetate); 1 H NMR (400MHz, d 6 -acetone) δ7.72(d, J=8.4Hz, 1H), 7.61(d, J=8.4Hz, 2H), 7.44(dd, J=7.6, 0.4Hz, 1H), 7.36-7.30(m, 1H ), 7.26(d, J=8.0Hz, 2H), 7.11-7.05(m, 1H), 5.48(d, J=2.0Hz, 1H), 4.99(d, J=2.0Hz, 1H), 4.80-4.75 (m, 1H), 2.31(s, 3H), 2.12-2.04(m, 1H), 1.86-1.76(m, 1H), 1.47-1.21(m, 10H), 0.86(t, J=6.8Hz, 3H ); 13 C NMR (100.5MHz, d 6 -acetone) δ146.1, 145.1, 144.9, 135.4, 131.3, 130.8, 130.4, 128.1, 125.3, 1...

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Abstract

The invention relates to a beta-naphthyl methyl substituted spiral bisoxazoline ligand, a synthetic method and an application. The ligand has the advantages of simple synthetic method, mild condition and applicability for industrialization production. The ligand has a spiral framework and a feature of a plurality of chiral centers, therefore the ligand has high catalytic activity and chiral induction effect and strong adjustment capacity in an asymmetric catalytic reaction of transition metals. Pyrrolidine derivants with various optical activities are prepared through high region selectivity and high enantioselectivity from allenoic and o-iodoaniline by the catalysis of the ligand. With the important biological activity, the pyrrolidine derivant has a better prospect of industry and medicine applications.

Description

technical field [0001] The invention relates to a spirocyclic bisoxazoline ligand substituted by β-naphthylmethyl, a synthesis method and application thereof. Under the catalysis of the ligand, various optically active indole derivatives can be prepared from allene and o-iodoaniline with high regioselectivity and high enantioselectivity. Background technique [0002] Chiral indoles are an important class of molecular skeletons, which are contained in many natural products and alkaloids. However, the synthesis of such important frameworks through catalyzed asymmetric reactions is a challenging task. Trost, B.M. reported in J.Am.Chem.Soc.2006, 128, 6314 the asymmetric allyl substitution reaction of indole to synthesize 3-substituted indolane derivatives. Fu, G.C. in J.Am.Chem.Soc. 2006, 128, 14264 gave optically active indolane products by asymmetric hydrogenation of indoles. [0003] At the same time, chiral bisoxazoline ligands are a very important class of ligands. Since...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D263/12B01J31/22C07D209/08C07D209/48C07D209/12C07B53/00
Inventor 舒伟麻生明
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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